The present invention relates to a compound comprising calcium or magnesium acetylacetonate at least partially coated with a compatibilising agent, and to its production.
It also relates to the use of the compound as an additive in formulations based on halogenated polymers.
Calcium acetylacetonate figures among the most common thermal stabilising agents for formulations comprising halogenated polymers, more particularly polyvinyl chloride.
However, while it has been clearly established that halogenated polymer formulations can be effectively stabilised as regards temperature, the use of such stabilised polymers still presents a few problems. It has been shown that the presence of just such a chelate is the cause of defects in the formed polymer. More particularly, it has been noted that the articles obtained can have heterogeneities appearing as dimples, grains or even pits.
These very difficulties are expected with a magnesium acetylacetonate.
One aim of the present invention is thus to propose a solution to the problems of heterogeneities appearing when forming formulations based on halogenated polymer(s) and stabilised by calcium or magnesium acetylacetonate.
It has unexpectedly been discovered that an association of calcium or magnesium acetylacetonate with a particular compound coating at least a portion of said chelate can eliminate the above-mentioned problems with heterogeneities in the polymeric formulation. In this respect, the compound which at least partially coats the chelate can render the calcium or magnesium acetylacetonate compatible with the formulation.
It should be noted that coating can also act to render the calcium or magnesium acetylacetonate water-repellent, reducing or even eliminating the take-up of moisture by these compounds. In this manner, the service properties of the final polymeric formulation, such as weld strength, are improved as a result.
Finally, coating can improve the dispersion of calcium or magnesium acetylacetonate in the formulation comprising the halogenated polymer.
Thus in a first aspect, the present invention is constituted by a compound comprising calcium or magnesium acetylacetonate partially or completely coated with at least one compatibilising agent selected from:
alcohols containing 12 to 30 carbon atoms, which may or may not be saturated;
carboxylic or sulphonic acids containing 12 to 30 carbon atoms, which may or may not be saturated, substituted or not substituted by at least one hydroxyl group, or derivatives thereof;
phosphates or titanates comprising at least one chain containing 12 to 30 carbon atoms, which may or may not be saturated;
xcex2-diketone compounds with at least one chain containing at least 7 carbon atoms;
waxes;
polyols;
epoxided vegetable oils;
polysiloxane oils or resins, or silanes.
In a second aspect, the invention is constituted by a process for preparing the above additive, in which the calcium or magnesium acetylacetonate is brought into contact with at least one compatibilising agent, optionally in the form of a suspension or a dispersion.
The present invention also concerns the use of such a compound as an additive in formulations comprising at least one halogenated polymer.
Other characteristics and advantages of the present invention will become clear from the following description.
The metallic acetylacetonate used in the present invention corresponds to the following formula: [CH3COCHCOCH3]2M,xH2O, where x is in the range 0 to 2, and M represents calcium or magnesium. The present invention is particularly suitable for calcium acetylacetonate.
Calcium acetylacetonate is well known and available, for example, from Rhodia Chemie under the trade name Rhodiastab X7(copyright).
For simplification, the remainder of the disclosure will refer to the acetylacetonate alone, it being understood that this term covers both calcium acetylacetonate and magnesium acetylacetonate.
The scope of the present invention also encompasses the use of a combination of the two acetylacetonates.
The acetylacetonate is generally used in the form of a powder the grain size of which is in the range 3 to 200 xcexcm.
In accordance with one essential characteristic of the present invention, the acetylacetonate is partially or completely coated with at least one compatibilising agent.
More particularly, this compatibilising agent is selected from:
alcohols containing 12 to 30 carbon atoms, which may or may not be saturated;
carboxylic or sulphonic acids containing 12 to 30 carbon atoms, which may or may not be saturated, substituted or not substituted by at least one hydroxyl group, or derivatives thereof;
phosphates or titanates comprising at least one chain containing 12 to 30 carbon atoms, which may or may not be saturated;
xcex2-diketone compounds with at least one chain containing at least 7 carbon atoms;
waxes;
polyols;
epoxided vegetable oils;
polysiloxane oils or resins, or silanes.
Regarding the alcohols containing 12 to 30 carbon atoms, saturated or unsaturated aliphatic monoalcohols are particularly suitable. Non limiting examples which can be cited are lauric, myristic, stearic, isostearic, cetyl, behenic, lauroleic, oleic, erucic and linoleic alcohol, used alone or as a mixture.
Compatibilising agents which can be used in the present invention include carboxylic acids containing 12 to 30 carbon atoms, as well as derivatives thereof.
More particularly, the compatibilising agent can be a linear or branched aliphatic carboxylic acid containing 12 to 30 carbon atoms, which may or may not be saturated, optionally comprising one or more hydroxyl groups.
Agents of this type which can be mentioned include stearic, lauric, myristic, palmitic, oleic, ricinoleic and behenic (docosanoic) acid, linoleic acid, linolenic acid, ricinoleic acid, hydroxystearic acid, or any other acid originating from glycerides or triglycerides, natural or otherwise, suitable for carrying out the invention. The acids can be used alone or as a mixture.
Regarding the possible derivatives of these acids, esters of these acids can be cited, in particular esters obtained from monoalcohols containing 1 to 30 carbon atoms, or mono-or polyesters obtained from polyols, such as glycerol derivatives, or alkylene glycols such as propylene glycol.
The carboxylic acid salts cited above constitute a further class of derivatives of these acids. Salts of alkali metals, alkaline-earth metals, aluminium, lanthanum and zinc are particularly suitable. More particularly, sodium, calcium, magnesium, aluminium, lanthanum or zinc salts are used.
A suitable sulphonic acid which can be cited is dodecylbenzene sulphonic acid.
Compatibilising agents which can be used within the context of the present invention include xcex2-diketones with formula R1COCHR2COR3; where radical R1 represents a linear or branched, substituted or non substituted C7-C30 hydrocarbon radical, radical R3 represents a linear or branched, substituted or non substituted C1-C30 hydrocarbon radical, and radical R2 represents a hydrogen atom or a linear or branched C1-C4 hydrocarbon radical.
More particularly, radical R1 represents a linear or branched C7-C30 alkyl or alkenyl radical; radical R3 represents a linear or branched C1-C30 alkyl or alkenyl radical; a C6-C30 aryl radical, substituted or not substituted by at least one alkyl radical and/or a halogen atom and/or a silicon atom; a C3-C14 cycloaliphatic radical and can optionally comprise carbon-carbon double bonds. It should be noted that radicals R1 and R3 can be identical or different.
Preferably, radical R3 represents a linear or branched C1-C18 alkyl radical; a C6-C10 aryl radical, which may or may not be substituted by at least one alkyl radical and/or a halogen atom: or a C3-C14 cycloaliphatic radical and can optionally comprise carbon-carbon double bonds.
Radicals R1 and R3 which have just been described can optionally be modified (substituted) by the presence in the aliphatic chain or one or more groups with formula xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94.
Radical R2 can be either a hydrogen atom or a C1-C4 alkyl radical, the aliphatic chain of which can be interrupted (substituted) by one or more groups with formula xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94.
Preferably, R2 represents a hydrogen atom.
Suitable xcex2-diketones which can be cited include octanoylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane and lauroylbenzoylmethane.
Waxes which can be used as an acetylacetonate compatibilising agent which can be mentioned include montanate waxes, polyethylene waxes and their oxidised derivatives, and paraffins.
A further type of compatibilising agent is constituted by polyols where the hydroxyl functions are neighbouring (in the xcex1 or xcex2 position), or otherwise. These compounds can be used alone or as a mixture.
More particularly, polyols containing 2 to 32 carbon atoms can be used, carrying two to nine hydroxyl groups, and wherein the hydroxyl groups can readily be in the neighbouring position or not.
These compounds include C2-C32 diols such as propylene glycol, butylene glycol, butanediol, pentanediol, hexanediol, dodecanediol, neopentyl glycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerine, mixtures of oligomers and glycerine with a degree of polymerisation of 2 to 10, hydroxystearic alcohol, or ricinoleyl alcohol.
A further family of polyols which can readily be used is constituted by polyvinyl alcohols which may be partially acetylated.
It is also possible to use hydroxylated compounds comprising isocyanurate groups such as tris(2-hydroxyethyl)isocyanurate.
In a further possibility, the compatibilising agent is selected from epoxided vegetable oils such as epoxided soya oil, or epoxided castor oil.
A further type of compatibilising agent can be selected from polysiloxane oils or resins.
More particularly, polydialkylsiloxane oils or polyhydrogenoalkylsiloxane oils can be cited wherein the alkyl radical contains 1 to 3 carbon atoms, preferably a methyl radical.
These oils have the following general formula:
YOxe2x80x94[(R)Si(R)xe2x80x94O]xxe2x80x94Y, where radicals R, which can be identical or different, represent an alkyl radical containing 1 to 3 carbon atoms, preferably a methyl radical, or a hydrogen atom provided that only one of the two radicals is a hydrogen atom, Y represents a hydrogen atom or (Rxe2x80x2)3Si, where radicals Rxe2x80x2, which may be identical or different, represent an alkyl radical containing 1 to 3 carbon atoms, preferably methyl. The coefficient x can vary within a wide range, but more particularly it is in the range 5 to 300.
Functionalised polymethylsiloxane oils such as xcex3-hydroxypropylene oils are also suitable.
Finally, as regards the polysiloxane resins, resins obtained by the action of polyhydrogenosiloxane oils on polysiloxane oils carrying vinyl groups in the presence of a platinum based catalyst are more particularly used.
It is also possible to use polysiloxane resins obtained by hydrolysis and self-condensation of at least one silane with formula (RO)3SiF or (RO)2(Me)SiF where R, which may be identical or different, represents an alkyl radical containing 1 to 4 carbon atoms; more particularly, F represents the following radicals:
xe2x80x94CHxe2x95x90CH2;
xe2x80x94(CH2)3OH;
xe2x80x94(CH2)3xe2x80x94NH2;
xe2x80x94(CH2)3NHCH2CH2NH2; 
xe2x80x94(CH2)3Oxe2x80x94COxe2x80x94CHxe2x95x90CH2;
xe2x80x94(CH2)3Oxe2x80x94COxe2x80x94(CH3)CHxe2x95x90CH2.
It is also possible to use the silanes cited above as compatibilising agents.
In accordance with the present invention, the compatibilising agent can be used alone or in the form of any mixture of a plurality of the possible agents cited above. In this case, two alternatives are possible: either a coating of acetylacetonate particles comprising a plurality of agents, or a mixture of particles each comprising a coating based on a single agent.
The proportion by weight of compatibilising agent with respect to the acetylacetonate (i.e., the calcium acetylacetonate or magnesium acetylacetonate) can fall within a wide range which can be as broad as 0.1% to 20% by weight with respect to the weight of the acetylacetonate. More particularly, the proportion of compatibilising agent is in the range 0.1% to 10% by weight with respect to the weight of acetylacetonate. Preferably, the proportion is in the range 0.1% to 5% by weight with respect to the same reference, and more advantageously in the range 0.1% to 2% by weight with respect to the same reference.
A process for preparing the additive of the invention will now be described.
Conventional coating processes can be used to prepare the compound of the invention.
Thus the compound of the invention can be obtained by bringing calcium or magnesium acetylacetonate into contact with at least one compatibilising agent, optionally in the presence of a solvent and/or a dispersing agent.
It should be noted that the solvent and/or dispersing agent used does not dissolve the calcium or magnesium acetylacetonate.
Normally, the solvent or dispersing agent for the compatibilising agent, if such a solvent or dispersing agent is present, is selected from water, C1-C5 monoalcohols, in particular methanol or ethanol, C2-C6 ethers such as dimethylether, methylethylether, diethylether and hydrocarbons such as hexane. Mixtures of these solvents/dispersing agents are, of course, possible.
In a first variation, which can be termed dry impregnation, the quantity of solvent/dispersing agent is such that the limit of the absorption capacity of the calcium or magnesium acetylacetonate is not exceeded. The skilled person will readily be able to determine the optimum quantity of solvent/dispersing agent for the operating conditions (quantity, grain size, suspension of the acetylacetonate, quantity of compatibilising agent).
In a further implementation of this variation, the compatibilising agent is brought into contact with the acetylacetonate in the absence of a solvent or dispersing agent.
Contact with the acetylacetonate, in one or other implementation indicated above (presence or absence of solvent/dispersing agent) preferably takes place so as to control, preferably to avoid any agglomeration of the particles with themselves. As a result, in this first variation, it is preferable to introduce the compatibilising agent into the acetylacetonate.
This contact can be achieved using a burette or any similar introduction means. It can also be achieved using a sprayer provided with a nozzle.
Contact obviously takes place with stirring, whether caused by mechanical stirring or using a rotating drum, or a granulator.
The operating period depends on many criteria. In general, however, it lasts until a macroscopically homogeneous mixture is obtained, in other words a mixture which is free of visible aggregates.
In a second variation, the quantity of solvent used is such that it dissolves the desired quantity of compatibilising agent. Here again, the skilled person can determine this quantity using general knowledge. In this second variation, dispersions of acetylacetonate in a solution of compatibilising agent(s) are obtained conventionally. It should be noted that a fraction of compatibilising agent can always be found in the form of a dispersion.
Contact in this variation can take place by introducing the acetylacetonate into the solution or vice versa, or even by bringing the two into contact simultaneously.
This contact takes place with mechanical stirring, if necessary completed by using ultrasound.
Whatever the variation used, contact preferably takes place at ambient temperature while higher temperatures are not excluded.
The contact operation advantageously takes place in air.
In general, once the acetylacetonate and the compatibilising agent have been brought into contact, drying is carried out. Drying can take place at ambient temperature, by oven drying or by evaporating off the solvent/dispersing agent if present, under vacuum or otherwise. Preferably, and this is particularly applicable in the second variation, drying is carried out so as to avoid too rapid a loss of solvent/dispersing agent, which would result in agglomerating the particles together.
The duration of the drying operation is normally in the range from a few minutes to about 12 hours.
Optionally, and if necessary, before introducing it into the polymeric formulation, the coated product can be lightly ground in order to deagglomerate the particles.
Clearly, this process is given solely by way of indication and any other method for coating a product by another can be used.
Thus as indicated above, the additive of the invention is more particularly intended for use in formulations comprising halogenated polymers. More particularly, the polymers in question are chlorinated polymers.
The invention is particularly suitable for stabilising formulations based on polyvinyl chloride (PVC).
The term xe2x80x9cpolyvinyl chloridexe2x80x9d means compositions the polymer of which is a vinyl chloride homopolymer. The homopolymer can be chemically modified, for example by chlorination.
Many vinyl chloride copolymers can also be stabilised using the composition of the invention. In particular, they are polymers obtained by copolymerisation of vinyl chloride with monomers with a polymerisable ethylene bond such as vinyl acetate, vinylidene chloride; maleic, fumaric acid or esters thereof; olefins such as ethylene, propylene or hexene; acrylic or methacrylic esters; styrene; vinyl ethers such as vinyldodecylether.
Normally, the copolymers contain 50% by weight of vinyl chloride motifs, preferably at least 80% by weight thereof.
PVC alone or mixed with other polymers is the chlorinated polymer which is the most widely used in the stabilised formulations of the invention.
In general, any type of polyvinyl chloride is suitable, regardless of the preparation mode. Thus polymers obtained, for example, by bulk, suspension, or emulsion processes can be stabilised using the composition of the invention, regardless of the intrinsic viscosity of the polymer.
The presence of the additive of the invention in the formulation can improve the compatibility of the acetylacetonate in said polymeric formulations, to avoid the problems of heterogeneity caused by the presence of the acetylacetonate alone, when using the formulation. It can also improve the dispersion of the acetylacetonate in the formulation.
The quantity of the additive of the invention, expressed as calcium or magnesium acetylacetonate, is in the range 0.01 to 5 g per 100 g of halogenated polymer, more particularly in the range 0.05 to 2 g with respect to the same reference.
The polymeric formulations can also comprise the usual additives in the field.
Thus the formulation can comprise at least one xcex2-diketone compound which can be in the free form or in the form of a metallic chelate or in the form of a combination of these two species.
Thus when the compound is in the free form, it corresponds to the following formula (1): R1COCHR2COR3: in which formula R1 and R3, which can be similar or different, each represent a linear or branched. substituted or non substituted C1-C30, hydrocarbon radical: R2 is a hydrogen atom or a linear or branched C1-C4 hydrocarbon radical.
When the xcex2-diketone compound is in the form of a metallic chelate, it can be represented by the following formula (II): 
where Mn+ represents at least one of the following metals: calcium, zinc, aluminium, magnesium or lanthanum, n being 2 or 3, R1, R3, which may be identical or different, linear or branched. substituted or not substituted, represent a C1-C30 hydrocarbon radical and R2 represents a hydrogen atom or a linear or branched C1-C4 hydrocarbon radical with the exception of calcium and magnesium acetylacetonates.
In a more particular implementation of the invention, the radicals R1 and R3, which may be identical or different, represent a linear or branched C1-C24 alkyl or alkonyl radical; a C6-C30 aryl radical which may or may not be substituted by at least one alkyl radical and/or a halogen atom and or a silicon atom: or a C3-C14 cycloaliphatic radical which can optionally comprise carbon-carbon double bonds.
It should be noted that if the xcex2-diketone compound is present in the two forms cited above, radicals R1 and R3 can differ from one product to the other.
Preferably, radicals R1 and R3, which may he identical or different, represent a linear or branched C1-C18 alkyl radical, a C6-C10 aryl radical, which may or may not be substituted by at least one alkyl radical and/or a halogen atom: or a C3-C14 cycloaliphatic radical, and can optionally comprise carbon-carbon double bonds.
In a further variation, radicals R1 and R3 can be bonded together so that the xcex2-diketone compound is in the form of a ring.
Radicals R1 and R3 described above can optionally be modified (substituted) by the presence in the aliphatic chain of one or more groups with formula xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94Coxe2x80x94.
Radical R2 can either be a hydrogen atom or a C1-C4 alkyl radical where the aliphatic chain can be interrupted by one or more groups with formula xe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94Oxe2x80x94, xe2x80x94COxe2x80x94.
Preferably, R2 represents a hydrogen atom.
The xcex2-diketone compounds can be obtained using conventional methods.
As an example, the xcex2-diketones can be synthesised by using a reaction for condensing an ester on a ketone, in the presence of an alkaline agent which can be an amide of a cation such as sodium, or hydrogen.
This reaction has been described in the following publication: R. HAUSER et al., xe2x80x9cThe acylation of ketones to form diketonesxe2x80x9d, Organic Reactionsxe2x80x94vol. VII, Chapter 3, p. 59-196, John WILEY, Ed. New York (1954), WIEDMAN et al., C. R. 238 (1954), p. 699, MORGAN et al., BER. 58 (1925), p. 333, LIVINGSTONE et al., Am. Soc. 46 (1924), p. 881-888, R. LEVINE et al., Am. Soc. 67 (1945), p. 1510-1517, and European patent EP-A-0 596 809.
Non limiting examples of xcex2-diketone compounds which are suitable for carrying out the invention which can be cited are octanoyl-benzoylmethane, stearoylbenzoylmethane, dibenzoylmethane or acetylbenzoylmethane, used alone or as a mixture. It should be noted that purified or non purified products can be used.
The following commercially available products can advantageously be used in the present invention: Rhodiastab 50(copyright), Rhodiastab X5(copyright), Rhodiastab X2(copyright), Rhodiastab 83(copyright), sold by Rhodia Chemie.
Compounds in the form of chelates are also known products and can be produced by reacting the appropriate xcex2-diketone with the above metal salts, such as chlorides, sulphates or nitrates, with oxides or hydroxides, with the metal itself, with carbonates or with alkoxides. It should be noted that these methods have been described in xe2x80x9cMetal xcex2-diketonates and allied derivativesxe2x80x9d by R. C. Mehrota, R. Gaur, D. P. Gaur, published in 1978 (Academic Press).
Chelates of octanoylbenzoylmethane, stearoylbenzoylmethane, dibenzoylmethane, acetylbenzoylmethane or acetylacetone (with the exception of calcium and magnesium acetylacetonates), used alone or as a mixture, can advantageously be used.
The total xcex2-diketone compound content, free and/or in the chelate form, is in the range 0.05 to 1 g per 100 g of halogenated polymer. Preferably, the xcex2-diketone content is in the range 0.1 to 0.5 g per 100 g of halogenated polymer.
Formulations based on a halogenated polymer can comprise at least one hydrochloric acid scavenger.
Hydrochloric acid scavenger compounds can be organic or mineral in type, and can be present alone or as a mixture.
More particularly, organic type hydrochloric acid scavengers include compounds comprising an alkaline-earth metal or a metal selected from columns IIB, IIA, IVB of the periodic table (from the supplement to the xe2x80x9cBulletin dxc3xa9 la Socixc3xa9txc3xa9 Chimique de France, no. 1. January 1966).
More particularly, cations are preferably selected from calcium, barium, magnesium, strontium, zinc, cadmium, tin or lead.
It should be noted that combinations can be envisaged such as a hydrochloric acid scavenger based on calcium and zinc, barium and zinc, or barium and cadmium, the first combination being preferred.
Regarding organic type hydrochloric acid scavengers comprising at least one of the elements from columns IIB and IIA, organic acid salts such as aliphatic or aromatic carboxylic acids, or fatty acids, or phenolates or aromatic alcoholates can be cited.
The most commonly used are, for example, salts of IIA or IIB elements of maleic, acetic, diacetic, propionic, hexanoic, 2-ethylhexanoic, decanoic, undecanoic, lauric, myristic, palmitic, stearic, oleic, ricinoleic, behenic (docosanoic), hydroxystearic, hydroxyundecanoic, benzoic, phenylacetic, para-tertiobutylbenzoic and salicylic acids, phenolates, alcoholates derived from naphthol or phenols substituted by one or more alkyl radicals, such as nonylphenols.
For practical or economic reasons, organic compounds of the alkaline-earth metals cited above which are preferably selected, are an alkaline-earth metal propionate, alkaline-earth metal oleate, alkaline-earth metal stearate, alkaline-earth metal laurate, alkaline-earth metal ricinoleate, alkaline-earth metal docosanoate, alkaline-earth metal benzoate, alkaline-earth metal para-tertiobutylbenzoate, alkaline-earth metal salicylate, alkaline-earth metal and mono(2-ethylhexyl)maleate, alkaline-earth metal nonylphenates, alkaline-earth metal naphthenate, and from the organic cadmium compounds cited above, cadmium propionate, cadmium 2-ethylhexanoate, cadmium laurate, cadmium stearate, cadmium salicylate, cadmium and mono(2-ethylhexyl)maleate, cadmium nonylphenates, cadmium naphthenate.
Regarding organic compounds comprising lead, those described in the xe2x80x9cENCYCLOPEDIA of PVCxe2x80x9d by Leonard I. NASS (1976) pages 299-303 can be cited.
These are constituted by a wide variety of compounds the most commonly used of which are dibasic lead carbonate, tribasic lead sulphate, tetrabasic lead sulphate, dibasic lead phosphite, lead orthosilicate, basic lead silicate, a co-precipitate of lead silicate and lead sulphate, basic lead chlorosilicate, a co-precipitate of silica gel and lead orthosilicate, dibasic lead phthalate, neutral lead stearate, dibasic lead stearate, tetrabasic lead fumarate, dibasic lead maleate, lead 2-ethylhexanoate, and lead laurate.
Regarding tin based compounds, reference should be made to the xe2x80x9cPLASTICS ADDITIVES HANDBOOKxe2x80x9d by GACHTER/MULLER (1985) pages 204-210 or the xe2x80x9cENCYCLOPEDIA OF PVCxe2x80x9d by Leonard I. NASS (1976) pages 313-325.
More particularly, they are mono-or dialkyltin carboxylates and mono-or dialkyltin mercaptides.
The most frequently used of these compounds are derivatives of di-n-methyltin, di-n-butyltim or di-n-octyltin such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin laurate-maleate, dibutyltin bis(mono-C4-C8 alkyl maleate), dibutyltin bis(laurylmercaptide), dibutyltin S-Sxe2x80x2(isooctylmercaptoacetate), dibutyltin xcex2-mercaptopropionate, polymeric di-n-octyltin maleate, bis-S-Sxe2x80x2(isooctyl mercaptoacetate)-di-n-octyltin, di-n-octyltin xcex2-mercaptopropionate. Monoalkylated derivatives of the above compounds are also suitable.
A mineral type hydrochloric acid scavenger which can also be cited is an aluminium and/or magnesium sulphate and/or carbonate, in particular of the hydrotalcite type. It should be remembered that hydrotalcite type compounds have the following formula: Mg1xe2x88x92xAlx(OH)2Anxe2x88x92x/nmH2O, where x is in the range 0 (excluded) to 0.5, Anxe2x88x92 represents an anion such as carbonate, nitrogen is from 1 to 3, and m is positive. It should be noted that products of this type which have undergone a surface treatment with an organic compound can be used. The scope of the present invention encompasses using a hydrotalcite type product doped with zinc, which has optionally undergone a surface treatment with an organic compound. Particular products of this type include Alcamizer(copyright)4 (sold by Kyowa).
It is also possible to use essentially amorphous compounds with formula (MgO)y, Al2O3, (CO2)x, (H2O)z, in which x, y and z satisfy the following inequalities: 0 less than xc3x97xe2x89xa60.7; 0 less than yxe2x89xa61.7 and zxe2x89xa73. These compounds are described in European patent EP-A-0 509 864. Further, compounds known as catoites with formula Ca3Al2(OH)12 or Ca3Al2(SiO)4(OH)12 are suitable as min hydrochloric acid scavengers.
Formulations based on halogenated polymers can comprise titanium dioxide.
Preferably, the titanium dioxide is in the rutile form.
In general, the grain size of the titanium dioxide in the stabilising compositions of the invention is in the range 0.1 to 0.5 xcexcm.
In one particular implementation of the invention, a titanium dioxide in the rutile form is used which has undergone a surface treatment, preferably a mineral surface treatment.
Non limiting examples of particularly suitable titanium dioxides which can be used in the present invention are titanium dioxide Rhoditan(copyright) RL 18, Rhoditan(copyright) RL90 sold by Rhodia Chimie and titanium dioxide Kronos 2081(copyright) and 2220(copyright) sold by KRONOS.
The halogenated polymer based formulations can also comprise other white or coloured pigments. Coloured pigments which can be cited include cerium sulphide.
It should be noted that the quantity of pigment introduced into the formulation can vary between wide limits and depends on the colouring power of the pigment and on the desired final coloration. However, as an example, the quantity of pigment can be between 0.1 and 20 g per 100 g of halogenated polymer, preferably 0.5 to 15 g with respect to the same reference.
The formulation can also comprise at least one polyol containing 2 to 32 carbon atoms and having two to nine hydroxyl groups.
These compounds include C3-C30 diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentylglycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerine and mixtures of glycerine oligomers with a degree of polymerisation of 2 to 10.
A further family of polyols which can suitably be used is constituted by partially acetylated polyvinyl alcohols.
Similarly, it is possible to use hydroxylated compounds comprising isocyanurate groups, used alone or in combination with the above polyols, such as tris(2-hydroxyethyl)isocyanurate.
The quantity of polyol used in generally in the range 0.05 to 5 g per 100 g of halogenated polymer. More particularly, it is less than 2 g per 100 g of halogenated polymer.
Optionally, compounds of the organic phosphite type such as trialkyl, aryl, triaryl, dialkylaryl, or diarylalkyl phosphites for which the term xe2x80x9calkylxe2x80x9d designates hydrocarbon groups of C8-C22 monoalcohols or polyols, and the term Aryl designates aromatic phenol or phenol groups substituted by C6-C12 alkyl groups, can be incorporated into the formulation. It is also possible to use calcium phosphites such as compounds of the type Ca(HPO3).(H2O) and phosphite-hydroxy-aluminium-calcium complexes.
The amount of additive of this type is normally in the range 0.1 to 2 g per 100 g of halogenated polymer.
The formulations can also comprise at least one crystalline synthetic alkali metal aluminosilicate with a water content in the range 13% to 25% by weight, with composition 0.7-1M2O.Al2O3.1.3-2.4 SiO2 where M represents an alkali metal such as sodium. Type NaA zeolites such as those described in United States patent U.S. Pat. No. 4,590,233 are also suitable.
The amount of this type of compound is generally in the range 0.1 to 5 g per 100 g of halogenated polymer.
The formulations can also comprise epoxy type compounds. These compounds are generally selected from epoxided polyglycerides or epoxided fatty acid esters, such as epoxided linseed oil, soya oil or fish oil.
The quantity of compounds of this type is normally in the range 0.5 to 10 g per 100 g of halogenated polymer.
Other conventional additives can complete the formulation, depending on the application for which it is intended.
As a general rule, the formulation can comprise phenolic antioxidants, anti-UV agents such as 2-hydroxybenzophenones or 2-hydroxybenzotriazoles, or sterically hindered amines which are generally known as Hals.
The amount of this type of additive is generally in the range 0.05 to 3 g per 100 g of halogenated polymer.
If necessary, lubricants which aid processing can also be used, selected from glycerol monostearates or propylene glycol, fatty acids or esters thereof, montanate waxes, polyethylene waxes or their oxidised derivatives, paraffins, metallic soaps and functionalised polymethylsiloxane oils such as xcex3-hydroxypropylenated oils.
The quantity of lubricant in the halogenated polymer based formulation is generally in the range 0.05 to 2 g per 100 g of halogenated polymer.
The formulation can also comprise plasticizers selected from alkyl phthalates. The most generally used compounds are selected from di(2-ethylhexyl)phthalate, linear C6-C12 dibasic acid esters, trimellitates or phosphate esters.
The quantity of plasticizer used in the formulations falls within a wide range depending on the rigid or flexible nature of the final polymer. By way of indication, the amount is in the range 0 to 100 g per 100 g of polymer.
The formulations can be prepared using any means known to the skilled person.
The various constituents can be incorporated into the polymer individually or after previously having prepared a mixture of a plurality of these constituents, such as the stabilising composition of the invention used alone or in the presence of a lubricant.
Conventional incorporation methods are perfectly suitable for producing the PVC based formulation.
Thus, and purely by way of indication, this operation can be carried out in a mixer provided with a system of paddles and counter-paddles operating at high speed.
In general, the mixing operation is carried out at a temperature of less than 130xc2x0 C.
Once the mixture has been produced, the composition is formed using methods normally used in the industry such as injection, extrusion blow-moulding, extrusion, calendering or rotational moulding.
The temperature at which forming is carried out is generally 150xc2x0 C. to 220xc2x0 C.
Some non limiting examples will now be described.